Adhesives are made up of various components such as polymers, tackifiers, waxes and oils. Adhesive formulations based on these ingredients are susceptible to degradation. The consequences of degradation are discoloration, loss of elongation, loss of tensile strength, loss of tack and change in viscosity, molecular weight and molecular weight distribution. Degradation can be caused by prolonged exposure to sunlight. Sunlight contains invisible ultraviolet (UV) radiation with wavelengths between 290 and 400 nm. This radiation is responsible for the initiation of photodegradation.
Absorption of UV light by chromophores present in the adhesive formulation transforms the chromophores into their excited states which can undergo further undesired reactions. Some polymers contain strongly absorbing chromophores as a major part of their structures. Other polymers contain unintentional impurities such as ketones and hydroperoxide moieties and catalyst residues which act as chromophores. Absorption of UV radiation by these chromophores eventually results in bond cleavage, chain scission and/or crosslinking reactions.
Photostabilization of adhesives can be achieved by the addition of UV absorbers which convert the absorbed energy into harmless heat. An ideal UV absorber should be extremely photostable and have strong absorption over the UV range from 290 to 400 nm, but particularly the range of 350 to 400 nm. Classes of UV absorbers include the salicylates, cyanoacrylates, malonates, oxanilides, benzophenones, s-triazines and benzotriazoles.
Salicylates, cyanoacrylates, malonates and oxanilides absorb UV light primarily at the lower wavelengths of the UV range. These compounds have little to no absorption in the range of 350 to 400 nm which make them unsuitable for the instant applications. Benzophenones absorb over the lower half of the UV range, and they tend to be prone to yellowing upon light exposure due to photodegradation. Recently, it has been shown photochemically that benzophenones decompose prematurely in ethylene-vinyl acetate encapsulants which lead to the production of polyenic chromophores. This color generation from light yellow to brown is not only highly undesirable and unsightly in adhesive systems, but also can results in a loss of adhesive properties. By contrast, selected benzotriazole UV absorbers are particularly useful because of their increased photostability.
Some polymers such as polycarbonates, polyesters and aromatic polyurethanes contain strongly absorbing chromophores as a major and integral part of their structures. Poly(ethylene terephthalate) (PET) and poly(ethylene 2,6-naphthalenedicarboxylate) (PEN) are particular examples the latter of which absorbs into the red UV region and especially need red-shifted benzotriazoles for UV protection. U.S. Pat. No. 5,294,473 and WO 98/34981 teach the use of coatings containing UV absorbers including some benzotriazoles in stabilizing PEN films. Adding an adhesive UV screening layer containing the benzotriazoles, especially those described in the instant invention, further protects such polymers in multilayered constructions and articles.
The description, preparation and uses of the 2H-benzotriazole UV absorbers are described in U.S. Pat. Nos. 3,004,896; 3,055,896; 3,072,585; 3,074,910; 3,189,615; 3,230,194; 4,127,586; 4,226,763; 4,278,589; 4,315,848; 4,383,863; 4,675,352; 4,681,905 and 4,853,471.
Selected benzotriazoles with just hydrogen or halogen at the 5-position of the benzo ring are photostable and soluble in adhesive formulations. One such benzotriazole is 2-(2-hydroxy-3-.alpha.-cumyl-5-tert-octylphenyl)-2H-benzotriazole as described in U.S. Pat. Nos. 5,554,760; 5,563,242; 5,574,166 and 5,607,987. These patents are incorporated herein by reference. While the absorbance of this benzotriazole is not red-shifted toward longer UV wavelengths, it is very photostable and is amazingly soluble in adhesives making it especially well-suited for the instant applications.
It is known in the art that the concomitant use of a hindered amine light stabilizer with a UV absorber such as a benzotriazole provides excellent stabilization in many polymer compositions as summarized by G. Berner and M. Rembold, "New Light Stabilizers for High Solids Coatings", Organic Coatings and Science and Technology, Vol. 6, Dekkar, New York, pp 55-85.
The effect of UV light on laminated articles that are exposed to the sun or other sources of UV light are of great concern to the manufacturers of such articles. Over time, constant or repeated exposure to UV light can result in dye and/or pigment fade for dyes and/or pigments used in such articles and in the degradation or breakdown of the adhesives, polymers or other materials used in the construction of the articles. The aforementioned fading and degradation shorten the useful life of the articles in question, making protection from UV light exposure an issue of great importance to the manufacturers of such articles.
Molecules known as UV absorbers are generally known in the art. However, due to the differences discussed above between the various UV absorber classes, it is the benzotriazoles and articles containing them which will be discussed here. Due to the incompatibility and low solubility of certain benzotriazoles, a need exists for a benzotriazole that is highly soluble and which is very photostable.
In addition, articles which incorporate the selected benzotriazoles of the instant invention are useful in protecting interior structures, textiles and fabrics from UV induced photodegradation such as in automotive applications.
International application WO 97/32225 describes the use of PEN films having reflective and polarizing elements for use as optical films.
U.S. Pat. No. 5,770,114 discloses stabilized compositions containing soluble benzotriazoles that are used in electrochromic devices. This patent discloses that 2-(2-hydroxy-5-methylphenyl)-2H-benzotriazole is effective in stabilizing such electrochromic devices against degradation from UV radiation, but that it is not soluble enough in aprotic solvents, e.g. propylene carbonate, to provide suitable protection for electrochromic devices for very long periods of time. This indicates that the acceptable benzotriazole UV absorbers must also exhibit excellent solubility in substrates and solvents in order to be acceptable.
Articles which would benefit from the incorporation of the instant, highly soluble and photostable benzotriazole include, but are not limited to:
(a) Retroreflective Sheets and Signs and Conformable Marketing Sheets as seen in WO 97/42261; and U.S. Pat. No. 5,387,458 which is incorporated herein by reference; PA1 (b) Solar Control Films of Various Construction as seen in British 2,012,668; European 355,962; and U.S. Pat. Nos. 3,290,203; 3,681,179; 3,776,805 and 4,095,013 which are incorporated herein by reference; PA1 (c) Corrosion Resistant Silver Mirrors and Solar Reflectors as seen in U.S. Pat. No. 4,645,714 which is incorporated herein by reference; PA1 (d) Reflective Print Labels as seen in U.S. Pat. No. 5,564,843 which is incorporated herein by reference; PA1 (e) UV Absorbing Glasses and Glass Coatings as seen in U.S. Pat. Nos. 5,372,889; 5,426,204; 5,683,804 and 5,618,626 which are incorporated herein by reference; PA1 (f) Electrochromic Devices as seen in European 752,612 A1; and U.S. Pat. Nos. 5,239,406; 5,523,877 and 5,770,114 which are incorporated herein by reference; PA1 (g) Films/Glazings as seen in WO 92/01557; Japanese Nos. 75-33286; 93-143668; 95-3217 and 96-143831; and U.S. Pat. No. 5,643,676 which is incorporated herein by reference; PA1 (h) Windscreens and Intermediate Layers as seen in Japanese Nos. 80-40018; 90-192118; 90-335037; 90-335038; 92-110128 and 94-127591; and PA1 (i) Optical Films as seen in WO 97/32225; and U.S. Pat. Nos. 4,871,784 and 5,217,794 which are incorporated herein by reference. PA1 (a) an adhesive; and PA1 (b) an effective stabilizing amount of a highly soluble and photos table benzotriazole which is 2-(2-hydroxy-3-.alpha.-cumyl-5-tert-octylphenyl)-2H-benzotriazole, 5-chloro-2-(2-hydroxy-3-.alpha.-cumyl-5-tert-octylphenyl)-2H-benzotriazole , 5-fluoro-2-(2-hydroxy-3-.alpha.-cumyl-5-tert-octylphenyl)-2H-benzotriazole , 2-(2-hydroxy-3-.alpha.-cumyl-5-tert-butylphenyl)-2H-benzotriazole, 5-chloro-2-(2-hydroxy-3-.alpha.-cumyl-5-tert-butylphenyl)-2H-benzotriazole or 5-fluoro-2-(2-hydroxy-3-.alpha.-cumyl-5-tert-butylphenyl)-2H-benzotriazole ; PA1 with the proviso that the benzotriazole in component (b) exhibits enhanced durability and low loss of absorbance when exposed to actinic radiation as witnessed by an absorbance loss of less than 0.5 absorbance units after exposure for 893 hours or less than 0.8 absorbance units after exposure for 1338 hours in a Xenon Arc Weather-Ometer. PA1 (a) an adhesive; and PA1 (b) an effective stabilizing amount of a combination of PA1 with the proviso that the benzotriazole in component (b) exhibits enhanced durability and low loss of absorbance when exposed to actinic radiation as witnessed by an absorbance loss of less than 0.5 absorbance units after exposure for 893 hours or less than 0.8 absorbance units after exposure for 1338 hours in a Xenon Arc Weather-Ometer. PA1 (a) an adhesive; and PA1 (b) an effective stabilizing amount of a combination of PA1 with the proviso that formula I does not represent 5-ethylsulfonyl-2-(2-hydroxy-5-methylphenyl)-2H-benzotriazole; 5-fluoro-2-(2-hydroxy-3-.alpha.-cumyl-5-tert-octylphenyl)-2H-benzotriazole ; 5-fluoro-2-(2-hydroxy-3-.alpha.-cumyl-5-tert-butylphenyl)-2H-benzotriazole ; 5-chloro-2-(2-hydroxy-3-.alpha.-cumyl-5-tert-octylphenyl)-2H- benzotriazole; 5-chloro-2-(2-hydroxy-3-.alpha.-cumyl-5-tert-octylphenyl)-2H-benzotriazole ; 5-chloro-2-(2-hydroxy-3,5-di-tert-butylphenyl)-2H-benzotriazole; or 5-chloro-2-(2-hydroxy-3-tert-butyl-5-methylphenyl)-2H-benzotriazole; and PA1 with the further proviso that the benzotriazole in component (b) exhibits enhanced durability and low loss of absorbance when exposed to actinic radiation as witnessed by an absorbance loss of less than 0.5 absorbance units after exposure for 893 hours or less than 0.8 absorbance units after exposure for 1338 hours in a Xenon Arc Weather-Ometer. PA1 (a) 5-trifluoromethyl-2-(2-hydroxy-3-.alpha.-cumyl-5-tert-octylphenyl)-2H-benz otriazole; PA1 (b) 5-trifluoromethyl-2-(2-hydroxy-5-tert-octylphenyl)-2H-benzotriazole; PA1 (c) 5-trifluoromethyl-2-(2-hydroxy-3,5-di-tert-octylphenyl)-2H-benzotriazole; PA1 (d) 2,2'-methylene-bis[6-(5-trifluoromethyl-2H-benzotriazol-2-yl)-4-tert-octyl phenol]; PA1 (e) methylene-2-[4-tert-octyl-6-(2H-benzotriazol-2-yl)phenol]2'-[4-tert-octyl- 6-(5-trifluoromethyl-2H-benzotriazol-2-yl)phenol]; PA1 (f) 3-(5-trifluoromethyl-2H-benzotriazol-2-yl)-5-tert-butyl-4-hydroxyhydrocinn amic acid; PA1 (g) methyl 3-(5-trifluoromethyl-2H-benzotriazol-2-yl)-5-tert-butyl-4-hydroxyhydrocinn amate; PA1 (h) isooctyl 3-(5-trifluoromethyl-2H-benzotriazol-2-yl)-5-tert-butyl-4-hydroxyhydrocinn amate; PA1 (i) 5-trifluoromethyl-2-[2-hydroxy-5-(3-hydroxypropyl)phenyl]-2H-benzotriazole ; PA1 (j) 5-butylsulfonyl-2-(2-hydroxy-3-.alpha.-cumyl-5-tert-octylphenyl)-2H-benzot riazole; PA1 (k) 5-octylsulfonyl-2-(2-hydroxy-3,5-di-.alpha.-cumylphenyl)-2H-benzotriazole; PA1 (l) 5-dodecylsulfonyl-2-(2-hydroxy-3,5-di-tert-butylphenyl)-2H-benzotriazole; PA1 (m) 5-octylsulfonyl-2-(2-hydroxy-3,5-di-tert-octylphenyl)-2H-benzotriazole; PA1 (n) 5-trifluoromethyl-2-(2-hydroxy-3-.alpha.-cumyl-5-tert-butylphenyl)-2H-benz otriazole; PA1 (o) 5-trifluoromethyl-2-(2-hydroxy-3-.alpha.-cumyl-5-nonylphenyl)-2H-benzotria zole; PA1 (p) 5-trifluoromethyl-2-[2-hydroxy-3-.alpha.-cumyl-5-(2-hydroxyethyl)phenyl]-2 H-benzotriazole; PA1 (q) 5-trifluoromethyl-2-[2-hydroxy-3-.alpha.-cumyl-5-(3-hydroxypropyl)phenyl]- 2H-benzotriazole; PA1 (r) 5-trifluoromethyl-2-(2-hydroxy-3,5-di-tert-amylphenyl)-2H-benzotriazole; PA1 (s) 5-trifluoromethyl-2-(2-hydroxy-3,5-di-tert-butylphenyl)-2H-benzotriazole; PA1 (t) 5-trifluoromethyl-2-(2-hydroxy-3-dodecyl-5-methylphenyl)-2H-benzotriazole; PA1 (u) 5-trifluoromethyl-2-[2-hydroxy-3-tert-butyl-5-(3-hydroxypropyl)phenyl]-2H- benzotriazole; PA1 (v) 5-trifluoromethyl-2-[2-hydroxy-3-tert-butyl-5-(2-hydroxyethyl)phenyl]-2H-b enzotriazole; PA1 (w) 5-trifluoromethyl-2-[2-hydroxy-5-(2-hydroxyethyl)phenyl]-2H-benzotriazole; PA1 (x) 5-trifluoromethyl-2-(2-hydroxy-3,5-di-.alpha.-cumylphenyl)-2H-benzotriazol e; PA1 (y) 5-fluoro-2-(2-hydroxy-3,5-di-.alpha.-cumylphenyl)-2H-benzotriazole; PA1 (z) 5-butylsulfonyl-2-(2-hydroxy-3,5-di-.alpha.-cumylphenyl)-2H-benzotriazole; PA1 (aa) 5-butylsulfonyl-2-(2-hydroxy-3,5-di-tert-butylphenyl)-2H-benzotriazole; PA1 (bb) 5-butylsulfonyl-2-(2-hydroxy-3,5-di-tert-octylphenyl)-2H-benzotriazole; PA1 (cc) 5-phenylsulfonyl-2-(2-hydroxy-3,5-di-tert-butylphenyl)-2H-benzotriazole; and PA1 (dd) 5-chloro-2-(2-hydroxy-3,5-di-.alpha.-cumylphenyl)-2H-benzotriazole. PA1 (a) 5-trifluoromethyl-2-(2-hydroxy-3-.alpha.-cumyl-5-tert-octylphenyl)-2H-benz otriazole; PA1 (b) 5-trifluoromethyl-2-(2-hydroxy-5-tert-octylphenyl)-2H-benzotriazole; PA1 (c) 5-trifluoromethyl-2-(2-hydroxy-3,5-di-tert-octylphenyl)-2H-benzotriazole; PA1 (g) methyl 3-(5-trifluoromethyl-2H-benzotriazol-2-yl)-5-tert-butyl-4-hydroxyhydrocinn amate; PA1 (j) 5-butylsulfonyl-2-(2-hydroxy-3-.alpha.-cumyl-5-tert-octylphenyl)-2H-benzot riazole; PA1 (n) 5-trifluoromethyl-2-(2-hydroxy-3-.alpha.-cumyl-5-tert-butylphenyl)-2H-benz otriazole; PA1 (s) 5-trifluoromethyl-2-(2-hydroxy-3,5-di-tert-butylphenyl)-2H-benzotriazole; PA1 (x) 5-trifluoromethyl-2-(2-hydroxy-3,5-di-.alpha.-cumylphenyl)-2H-benzotriazol e; PA1 (aa) 5-butylsulfonyl-2-(2-hydroxy-3,5-di-tert-butylphenyl)-2H-benzotriazole; and PA1 (cc) 5-phenylsulfonyl-2-(2-hydroxy-3,5-di-tert-butylphenyl)-2H-benzotriazole. PA1 (a) Retroreflective Sheets and Signs and Conformable Marketing Sheets; PA1 (b) Solar Control Films of Various Construction; PA1 (c) Corrosion Resistant Silver Mirrors and Solar Reflectors; PA1 (d) Reflective Print Labels; PA1 (e) UV Absorbing Glasses and Glass Coatings; PA1 (f) Electrochromic Devices; PA1 (g) Films/Glazings; PA1 (h) Windscreens and Intermediate Layers; and PA1 (i) Optical Films. PA1 (a) Retroreflective Sheets and Signs and Conformable Marketing Sheets; PA1 (b) Solar Control Films of Various Construction; PA1 (e) UV Absorbing Glasses and Glass Coatings; PA1 (g) Films/Glazings; and PA1 (h) Windscreens and Intermediate Layers. PA1 (b) Solar Control Films of Various Construction; or PA1 (h) Windscreens and Intermediate Layers. PA1 (i) Pressure Sensitive Adhesives; PA1 (ii) Rubber-Based Adhesives; PA1 (iii) Solvent and/or Emulsion Based Adhesives; PA1 (iv) Hot Melt Adhesives; and PA1 (v) Natural Product Based Adhesives. PA1 (i) Polyurethanes; PA1 (ii) Polyacrylics; PA1 (iii) Epoxys; PA1 (iv) Phenolics; PA1 (v) Polyimides; PA1 (vi) Poly(vinyl butyral); PA1 (vii) Polycyanoacrylates; PA1 (viii) Polyacrylates; PA1 (ix) Ethylene/acrylic acid copolymers and their salts (ionomers); PA1 (x) Silicon polymers; PA1 (xi) Poly(ethylene/vinyl acetate); PA1 (xii) Atatic polypropylene; PA1 (xiii) Styrene-diene copolymers; PA1 (xiv) Polyamides; PA1 (xv) Hydroxyl-terminated polybutadiene; PA1 (xvi) Polychloroprene; PA1 (xvii) Poly(vinyl acetate); PA1 (xviii) Carboxylated styrene/butadiene copolymers; PA1 (xix) Poly(vinyl alcohol); and PA1 (xx) Polyesters. PA1 (1) polyolefins; PA1 (2) mixtures of polyolefins; PA1 (3) copolymers of monoolefins and diolefins or other vinyl monomers; PA1 (4) polystyrene, poly(p-methylstyrene) or poly(.alpha.-methylstyrene); PA1 (5) copolymers of styrene or .alpha.-methylstyrene with dienes or acrylic derivative; PA1 (6) graft copolymers of styrene or .alpha.-methylstyrene; PA1 (7) halogen containing polymers; PA1 (8) polymers derived from .alpha.,.beta.-unsaturated acids and derivatives thereof; PA1 (9) copolymers of monomers of (8) with each other or other unsaturated monomers; PA1 (10) polymers derived from unsaturated alcohols and amines or the acyl derivatives or acetals thereof; PA1 (11) polyacetals such as polyoxymethylene and those polyoxymethylenes which contain ethylene oxide as a comonomer, polyacetals modified with thermoplastic polyurethanes, acrylates or MBS; PA1 (12) polyurethanes; PA1 (13) polyamides and copolyamides from diamines and dicarboxylic acids and/or from aminocarboxylic acids or the corresponding lactams; PA1 (14) polyureas or polyimides; PA1 (15) polyesters derived from dicarboxylic acids and diols and/or from hydroxycarboxylic acids or the corresponding lactones, especially poly(ethylene terephthalate) (PET) and poly(ethylene 2,6-naphthalenedicarboxylate) (PEN); PA1 (16) polycarbonates and polyester carbonates; PA1 (17) polysulfones and polyether sulfones; PA1 (18) crosslinked polymers derived from aldehydes on the one hand and phenols, ureas and melamines on the other hand; PA1 (19) unsaturated polyester resins derived from copolyesters of saturated and unsaturated dicarboxylic acids with polyhydric alcohols and vinyl compounds as crosslinking agents; PA1 (20) crosslinkable acrylic resins derived from substituted acrylates; PA1 (21) blends of the aforementioned polymers; PA1 (22) polysiloxanes; PA1 (23) polyketimines in combination with unsaturated acrylic polyacetoacetate resins or with unsaturated acrylic resins; PA1 (24) radiation curable compositions containing ethylenically unsaturated monomers or oligomers and a polyunsaturated aliphatic oligomer; and PA1 (25) ionomers (copolymers of ethylene/acrylic acid and their salts). PA1 poly(vinyl butyral), ethylene/vinyl acetate copolymers, polyacrylics, polyacrylates, natural rubber, polycyanoacrylates, poly(vinyl alcohol), styrene/butadiene rubber, phenolics, urea-formaldehyde polymers, epoxy resins, vinyl polymers, polyamides, polyurethanes, polyesters and styrene block copolymers. PA1 poly(vinyl butyral), ethylene/vinyl acetate copolymers, polyacrylics, polyacrylates, natural rubber, polycyanoacrylates, poly(vinyl alcohol), styrene/butadiene rubber, phenolics, vinyl polymers, polyurethanes and styrene block copolymers.